CN109134929B - Spiro intumescent flame retardant and preparation method thereof - Google Patents
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Abstract
本发明涉及一种螺环膨胀阻燃剂及其制备方法，属于含磷阻燃剂技术领域。分子式为C23H22O6N4P2，结构式是：一种螺环膨胀阻燃剂的制备方法为：将季戊四醇和刚蒸馏过的三氯氧磷加入至溶剂A中，先在室温下混合至体系稳定后，缓慢升温至一定温度，搅拌反应至无氯化氢气体放出，洗涤，抽滤，干燥，得中间体螺环磷酸酯二酰氯。将2‑苯基咪唑加入到溶剂B中，搅拌至澄清透明，再加入中间体螺环磷酸酯二酰氯，搅拌至体系混合均匀后，加入缚酸剂，反应结束后，洗涤，抽滤，干燥，得到螺环膨胀阻燃剂。本发明的一种螺环膨胀阻燃剂，熔点低(138℃)、与基体相容性好，阻燃效率高，在环氧树脂中，添加量为5％时，极限氧指数达到29.0％；垂直燃烧测试等级可达UL‑94V‑0级别。The invention relates to a spiro-ring expansion flame retardant and a preparation method thereof, belonging to the technical field of phosphorus-containing flame retardants. The molecular formula is C 23 H 22 O 6 N 4 P 2 , and the structural formula is: 
The preparation method of a spiro-ring expansion flame retardant is as follows: adding pentaerythritol and phosphorous oxychloride that has just been distilled into solvent A, first mixing at room temperature until the system is stable, slowly warming up to a certain temperature, and stirring the reaction until no reaction occurs. Hydrogen chloride gas is released, washed, filtered with suction, and dried to obtain the intermediate spirocyclic phosphate diacid chloride. Add 2-phenylimidazole to solvent B, stir until it is clear and transparent, then add the intermediate spirocyclic phosphate dichloride, stir until the system is evenly mixed, add acid binding agent, after the reaction is completed, wash, suction filtration, and dry , to obtain a spiro ring expansion flame retardant. The spiro-ring expansion flame retardant of the present invention has low melting point (138° C.), good compatibility with the matrix, and high flame retardant efficiency. In epoxy resin, when the addition amount is 5%, the limiting oxygen index reaches 29.0% ; The vertical combustion test level can reach UL‑94V‑0 level.
Description
Technical Field
The invention relates to a spiro-intumescent flame retardant and a preparation method thereof, belonging to the technical field of phosphorus-containing flame retardants.
Background
In the 21 st century, polymer materials have attracted extensive attention due to their light weight, low cost and high performance, and the development trend is to replace steel with plastics. However, the inherent flammability of polymer materials also brings great fire hazard, which causes huge economic loss and casualties, and people are constantly reminded of the necessity of flame retardant treatment of polymer materials, and the addition of flame retardants is one of the most effective means for improving flame retardant performance.
Although the halogen flame retardant has high flame retardant efficiency, mature application technology and moderate cost, the environmental protection requirements of people are stricter in recent years, and the influence of the halogen flame retardant on the ecological environment and the human health becomes the focus of attention. The combustion of the material emits a large amount of corrosive toxic gas, which can seriously corrode electronic and electrical systems and endanger human health and even life safety. The non-halogenation of flame retardants is therefore one of the important developments in the current field of flame retardancy.
Chinese patent application publication No. CN 102516304A discloses a class of phosphorus heterocyclic spiro compounds with flame retardant property and application of the compounds in epoxy resin preparation. But the melting point of the prepared flame retardant is over 260 ℃, and the flame retardant has the problem of poor compatibility with a matrix when added into epoxy resin, so that the flame retardant efficiency is influenced.
The flame retardant reported in the invention patent of Chinese patent application publication No. CN 104725665B is added into epoxy resin, when the addition amount is 10%, the UL-94 vertical combustion test reaches V-0 level, and the flame retardant efficiency is not high.
Disclosure of Invention
The invention aims to solve the problems of high melting point, poor compatibility with a matrix and large addition amount of the existing intumescent flame retardant, and provides a spiro intumescent flame retardant with a novel structure and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme.
A spiro-intumescent flame retardant with the molecular formula of C23H22O6N4P2The structural formula is:
a preparation method of a spiro intumescent flame retardant comprises the following specific steps:
step one, under the protection of nitrogen, pentaerythritol and phosphorus oxychloride which is distilled right now are added into a solvent A, the mixture is mixed at room temperature until the system is stable, the temperature is slowly raised to a certain temperature, the mixture is stirred to react until no hydrogen chloride gas is discharged, products are washed by dichloromethane, trichloromethane or acetone, the filtration is carried out, and then the products are dried in a vacuum oven at 85 ℃ for 12 hours, so that the intermediate spiro phosphate diacid chloride is obtained.
And step two, adding 2-phenylimidazole into a solvent B under the protection of nitrogen, stirring until the mixture is clear and transparent, adding the intermediate spiro phosphate diacyl chloride synthesized in the step one, stirring until the system is uniformly mixed, adding an acid binding agent, stirring and refluxing for 2-10 hours at 40-80 ℃, washing with trichloromethane after the reaction is finished, carrying out suction filtration, and carrying out vacuum drying for 6 hours at 50 ℃ to obtain yellowish powdery solid, thus obtaining the spiro expansion flame retardant.
The molar ratio of pentaerythritol to phosphorus oxychloride in the first step is 1: (3-7);
the solvent A in the step one is anhydrous acetonitrile or toluene;
the certain temperature in the step one corresponds to the solvent A, and the temperature is respectively 80 ℃ and 105 ℃;
and the solvent B in the step two comprises tetrahydrofuran and acetone.
The molar ratio of the spiro phosphate diacid chloride to the 2-phenylimidazole in the step two is 1: (2-3);
the acid-binding agent in the second step comprises triethylamine, cerium chloride, anhydrous potassium carbonate and pyridine; the molar ratio of the acid-binding agent to the spiro phosphate diacid chloride is 2: 1;
advantageous effects
1. The spiro intumescent flame retardant provided by the invention has the advantages of low melting point (138 ℃), good compatibility with a substrate and high flame retardant efficiency, and when the addition amount of the spiro intumescent flame retardant in epoxy resin is 5%, the limited oxygen index reaches 29.0%; the vertical burning test grade can reach UL-94V-0 grade.
2. The preparation method of the spiro intumescent flame retardant provided by the invention is simple, the reaction conditions are easy to control, and the yield of the flame retardant is high.
3. The spiro intumescent flame retardant provided by the invention is suitable for large-scale production and can realize industrialization.
Detailed Description
The following examples are given in conjunction with the experimental results of the present invention to further illustrate the invention
Example 1:
a spiro-intumescent flame retardant with the molecular formula of C23H22O6N4P2The structural formula is:
a preparation method of a spiro intumescent flame retardant comprises the following specific steps:
20.4g (0.15mol) of pentaerythritol were weighed into a 500mL four-necked flask, 69.3g (0.45mol) of freshly distilled phosphorus oxychloride and 80mL of anhydrous acetonitrile were added, and a thermometer, a mechanical stirrer, a condenser tube and a tail gas absorber were connected. Under the nitrogen atmosphere, the mixture is mixed at room temperature until the system is stable, then the temperature is slowly increased to 80 ℃, and the reaction is carried out until no HCl gas is released (the reaction is finished). And cooling to room temperature, carrying out suction filtration on the obtained precipitate, washing with dichloromethane or trichloromethane for several times, and carrying out vacuum drying at 85 ℃ for 12 hours to obtain 41.8g of a white powdery solid intermediate, namely the spiro phosphate diacid chloride, wherein the yield is 93.6%.
Weighing 17.3g (0.12mol) of 2-phenylimidazole according to a molar ratio of 1:2.2, adding the weighed 2-phenylimidazole into a 500mL four-neck flask with a thermometer, a mechanical stirrer, a condenser tube and a tail gas absorption device, stirring the mixture in 100mL tetrahydrofuran in the atmosphere of nitrogen until the mixture is clear and transparent, adding 14.9g (0.05mol) of spiro phosphate diacid chloride, stirring the mixture until the system is uniformly mixed, adding 14mL (0.1mol) of triethylamine, pre-reacting the mixture at 50 ℃ for 1h, slowly heating the mixture to 65 ℃, stirring the mixture for 6h to finish the reaction, carrying out suction filtration on a precipitate obtained by the reaction, washing the precipitate with trichloromethane, drying the precipitate at 50 ℃ for 6h in a vacuum oven, and obtaining 23.8g of yellowish solid after drying, wherein the yield is 93.1%.
The flame retardant in this example was applied to bisphenol a epoxy resin (E-44) and 4,4' -diaminodiphenylmethane was used as the curing agent to prepare a flame retardant epoxy resin. When the addition amount of the flame retardant is 5%, the limited oxygen index can reach 29.0%, the vertical combustion level can reach UL-94V-0 level, and the application requirements of the industrial flame-retardant epoxy resin are met.
Example 2:
a spiro-intumescent flame retardant with the molecular formula of C23H22O6N4P2The structural formula is:
a preparation method of a spiro intumescent flame retardant comprises the following specific steps:
40.8g (0.3mol) of pentaerythritol were weighed into a 500mL four-necked flask, 184.8g (1.2mol) of freshly distilled phosphorus oxychloride and 200mL of toluene were added, and a thermometer, a mechanical stirrer, a condenser and a tail gas absorber were connected. Under the nitrogen atmosphere, the mixture is mixed at room temperature until the system is stable, then the temperature is slowly raised to 105 ℃, and the reaction is carried out until no HCl gas is released (the reaction is finished). And cooling to room temperature, carrying out suction filtration on the obtained precipitate, washing with dichloromethane or trichloromethane for several times, and carrying out vacuum drying at 85 ℃ for 12 hours to obtain 83.9g of white powdery solid, namely the spiro phosphate diacid chloride, wherein the yield is 93.8%.
Weighing 69.2g (0.48mol) of 2-phenylimidazole according to a molar ratio of 1:2.4, adding the weighed 2-phenylimidazole into a 500mL four-neck flask with a thermometer, a mechanical stirrer, a condenser tube and a tail gas absorption device, stirring the mixture in 200mL tetrahydrofuran in the atmosphere of nitrogen until the mixture is clear and transparent, adding 29.8g (0.1mol) of spiro phosphate diacid chloride, stirring the mixture until the system is uniformly mixed, adding 49.4g (0.2mol) of cerium chloride, pre-reacting the mixture at 50 ℃ for 1h, slowly heating the mixture to 65 ℃, stirring the mixture for 8h, carrying out suction filtration on a precipitate obtained by reaction, washing the precipitate with trichloromethane, drying the precipitate at 50 ℃ for 6h in a vacuum oven, and obtaining 47.9g of yellowish solid after drying, wherein the yield is 93.5%.
Example 3:
a spiro-intumescent flame retardant with the molecular formula of C23H22O6N4P2The structural formula is:
a preparation method of a spiro intumescent flame retardant comprises the following specific steps:
68g (0.5mol) of pentaerythritol were weighed into a 1000mL four-necked flask, 285g (2.5mol) of freshly distilled phosphorus oxychloride and 400mL of toluene were added, and a thermometer, a mechanical stirrer, a condenser tube and a tail gas absorption device were connected. Under the nitrogen atmosphere, the mixture is mixed at room temperature until the system is stable, then the temperature is slowly increased to 90 ℃, and the reaction is carried out until no HCl gas is released (the reaction is finished). Cooling to room temperature, carrying out suction filtration on the obtained precipitate, washing with dichloromethane or trichloromethane for several times, and carrying out vacuum drying at 85 ℃ for 12 hours to obtain 140.0g of white powdery solid, namely the spiro phosphate diacid chloride, wherein the yield is 94.0%.
Weighing 75g (0.52mol) of 2-phenylimidazole according to a molar ratio of 1:2.6, adding the weighed 2-phenylimidazole into a 1000mL four-neck flask with a thermometer, a mechanical stirrer, a condenser tube and a tail gas absorption device, stirring in 400mL acetone in the atmosphere of nitrogen until the mixture is clear and transparent, adding 59.6g (0.2mol) of spiro-phosphate diacyl chloride, stirring until the system is uniformly mixed, adding 55.2g (0.4mol) of anhydrous potassium carbonate, pre-reacting for 1h at 40 ℃, slowly heating to 55 ℃, stirring for 10h, finishing the reaction, carrying out suction filtration on the precipitate obtained by the reaction, washing with trichloromethane, drying for 6h at 50 ℃ in a vacuum oven, and drying to obtain 96.0g of yellowish solid with the yield of 93.8%.
Example 4:
a spiro-intumescent flame retardant with the molecular formula of C23H22O6N4P2The structural formula is:
a preparation method of a spiro intumescent flame retardant comprises the following specific steps:
102g (0.75mol) of pentaerythritol were weighed into a 2000mL four-necked flask, 513g (4.5mol) of freshly distilled phosphorus oxychloride and 500mL of anhydrous acetonitrile were added, and a thermometer, a mechanical stirrer, a condenser tube and a tail gas absorber were connected. Under the nitrogen atmosphere, the mixture is mixed at room temperature until the system is stable, then the temperature is slowly increased to 80 ℃, and the reaction is carried out until no HCl gas is released (the reaction is finished). And cooling to room temperature, carrying out suction filtration on the obtained precipitate, washing with dichloromethane or trichloromethane for several times, and carrying out vacuum drying at 85 ℃ for 12 hours to obtain 210.3g of white powdery solid, namely the spiro phosphate diacid chloride, wherein the yield is 94.1%.
Weighing 121g (0.84mol) of 2-phenylimidazole according to a molar ratio of 1:2.8, adding the weighed 2-phenylimidazole into a 1000mL four-neck flask with a thermometer, a mechanical stirrer, a condenser tube and a tail gas absorption device, stirring in 400mL tetrahydrofuran in the atmosphere of nitrogen until the mixture is clear and transparent, adding 89.4g (0.3mol) of spiro-phosphate diacid chloride, stirring until the system is uniformly mixed, adding 84mL (0.6mol) of triethylamine, carrying out pre-reaction at 40 ℃ for 1h, slowly heating to 65 ℃, stirring for 10h, carrying out suction filtration on a precipitate obtained by reaction, washing with trichloromethane, drying in a vacuum oven at 50 ℃ for 6h, drying to obtain 143.9g of yellowish solid with the yield of 93.7%.
Example 5:
a spiro-intumescent flame retardant with the molecular formula of C23H22O6N4P2The structural formula is:
a preparation method of a spiro intumescent flame retardant comprises the following specific steps:
109g (0.8mol) of pentaerythritol were weighed into a 2000mL four-necked flask, 859g (5.6mol) of freshly distilled phosphorus oxychloride and 700mL of toluene were added, and a thermometer, a mechanical stirrer, a condenser tube and a tail gas absorber were connected. Under the nitrogen atmosphere, the mixture is mixed at room temperature until the system is stable, then the temperature is slowly raised to 105 ℃, and the reaction is carried out until no HCl gas is released (the reaction is finished). Cooling to room temperature, carrying out suction filtration on the obtained precipitate, washing with dichloromethane or trichloromethane for several times, and carrying out vacuum drying at 85 ℃ for 12h to obtain 225.5g of white powdery solid, namely the spiro phosphate diacid chloride, wherein the yield is 94.6%.
173g (1.2mol) of 2-phenylimidazole is weighed according to a molar ratio of 1:3, added into a 1000mL four-neck flask with a thermometer, a mechanical stirrer, a condenser tube and a tail gas absorption device, stirred in 600mL acetone in the atmosphere of nitrogen until the mixture is clear and transparent, then 119.2g (0.4mol) of spiro-phosphate diacid chloride is added, stirred until the system is uniformly mixed, 63.3g (0.8mol) of pyridine is added, the mixture is pre-reacted for 1h at 40 ℃, the temperature is slowly increased to 65 ℃, the reaction is ended after stirring for 9h, the precipitate obtained after the reaction is filtered, washed by trichloromethane, dried in a vacuum oven at 60 ℃ for 6h, 192.1g of yellowish solid is obtained after drying, and the yield is 93.8%.
The above detailed description is intended to illustrate the objects, aspects and advantages of the present invention, and it should be understood that the above detailed description is only exemplary of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
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